Alkali metal salts of cyclopentadienyl carboxylic acid manganese tricarbonyls and their free acids



United States Patent ALKALI METAL SALTS 0F CYCLOPENTADIENYL CARBOXYLICACID MANGANESE TRICARBON- THEIR FREE ACIDS John Kozikowski, Walled Lake,Mich., and Michael Cais, Haifa, Israel, assignors to Ethyl Corporation,New York, N.Y., a corporation of Virginia No Drawing. Originalapplication Aug. 12, 1960, Ser. No. 49,135. Divided and this applicationMay 13, 1963, Ser.

3 Claims. (Cl. 260429) This application is a division of applicationSer. No. 49,135, filed Aug. 12, 1960, now abandoned.

This invention relates to a variety of organometallic compounds and theprocesses employed in their production. More specifically, thisinvention relates to compounds and processes involving the use of acyclopentadienyl sulfonic acid manganese tricarbonyl compound.

An object of our invention is to provide new organometallic compoundsand processes for their preparation. A further object .is to providecyclopentadienyl manganese tricarbonyl derivatives and processes fortheir preparation. Additional objects will become apparent from areading of the specification and claims which follow.

The objects of this invention are accomplished by providing alkali metalsalts of cyclopentadienylcarboxylic acid manganese tricarbonyls and thecorresponding free acids obtained by acidifying said alkali metal salts.The alkali metal salts may be prepared from compounds having theformula:

These compounds are made, as in the case of the{{[(tricarbonylmanganese)cyclopentadienyl] carbonylmethylsulfonyl}cyclopentadienyl} manganese tricarbonyl, from reaction of the alkalimetal salt of a cyclopentadienyl sulfinic acid manganese tricarbonylWith an appropriate haloacylcyclopentadienyl manganese tricarbonylcompound. In the above formula, the group R is a univalent hydrocarbongroup, the group R is a divalent hydrocarbon group, and R is hydrogen orR, each hydrocarbon group containing from one to about eight carbonatoms, x is an integer ranging from zero to three, and y is either zeroor one. The above compounds are reacted With a base such as sodiumhydroxide and a hydroxyl-containing solvent such as Water or an alcoholsuch as ethanol to form a [(hydrocarbylsulfone) cyclopentdienyl]manganese tricarbonyl and the alkali metal salt of acyclopentadienylcarboxylic acid manganese tricarbonyl. These compoundshave the respective formulae:

SOaRr-CH Mn(C O);

' phate, trimethylphosphate 3,350,431 Patented Oct. 31, 1967 and II N

TR -C OM In the latter Formula H, M is an alkali metal.

In Formulae I and II, R is a hydrocarbon group containing from one toabout eight carbon atoms, x is an integer ranging from zero to three,and y is either zero or one.

The alkali metal salt of the cyclopentadienyl carboxylic acid manganesetricarbonyl is readily separated from the cyclopentadienyl sulfonemanganese tricarbonyl compound by means of extraction. The alkali metalsalt is then acidified to form the carboxylic acid compound which isinsoluble in an aqueous medium and can be filtered oil.

To further illustrate this embodiment of our invention, there ispresented the following example.

Example I Four grams of {{[(tricarbonylmanganese)cyclopentadienyl]carbonylmethylsulfonyl} cyclopentadienyl} manganese tricarbonyl, twograms of potassium hydroxide, 50 ml. of ethanol and 20 ml. of Water wererefluxed for 15 hours, cooled and poured into 400 ml. of water.Crystalline plates separated out and were filtered to yield 1.5 grams ofa solid which was identified as [(methylsulfonyl)cyclopentadienyl]manganese tricarbonyl.

The aqueous filtrate was acidified with hydrochloric acid and the solidwhich precipitated was filtered 01f. The solid precipitate wasrecrystallized from benzene to give 1.8 grams (93 percent yield) ofcyclopentadienyl carboxylic acid manganese tricarbonyl as yellowneedle-like crystals having a melting point of 194-195 C. The compoundwas identified by means of its infrared spectrum and analysis. Found:Mn, 22.1 percent. Calculated: Mn, 22.2 percent.

The preparation of {{[(tricarbonylmanganese)cyclopentadienyl]carbonylmethylsulfonyl} cyclopentadienyl} manganese tricarbonyl, thealkali metal salt of a cyclopentadienyl sulfinic acid manganesetricarbonyl, haloacylcyclopentadienyl manganese tricarbonyl, and otherrelated compounds is fully described in our copending application Ser.No. 283,139, filed May 13, 1965, now US. Patent No. 3,205,245, issuedSept. 7, 1965.

Among the important uses of our compounds is their use as fuel and oiladditives. For example, they are useful antiknocks when added togasoline. They may be used as primary antiknocks in which they are themajor antiknock component in the fuel or as supplemental antiknocks.When used as supplemental antiknocks, they are present as the minorantiknock component in the fuel in addition to a primary antiknock suchas a tetraalkyllead compound. Typical alkyllead compounds aretetraethyllead, tetrabutyllead, tetramethyllead and various mixed leadalkyls such as dimethyldiethyllead, diethyldibutyllead and the like.When used as either a supplemental or primary antiknock, our compoundsmay be present in the gasoline in combination with typical scavengerssuch as ethylene dichloride, ethylene dibromide, tricresylphosand thelike.

.as additives to residual and distillate fuels generally, e.g.,

jet fuels, home heater fuels and diesel fuels, to reduce smoke and/orsoot formation. Also, they may be employed as additives to lubricatingoils in which case they act to improve the lubricity of the base oil.

Our compounds are further useful in many metal plating applications. Inorder to effect metal plating using the compounds, they are decomposedin an evacuated space containing the object to be plated. Ondecomposition, they lay down a film of metal on the object. The gaseousplating may be carried out in the presence of an inert gas so as toprevent oxidation of the plating metal or the object to be plated duringthe plating operations.

The gaseous plating technique described above finds wide application informing coatings which are not only decorative but also protect theunderlying substrate material.

Deposition of metal on a glass cloth illustrates the applied process. Aglass cloth band weighing one gram is dried for one hour in an oven at150 C. It is then placed in a tube which is devoid of air and there isadded to the tube 0.5 gram of [(methylsulfonyl)cyclopentadienyl]manganese tricarbonyl. The tube is heated at 400 C. for one hour afterwhich time it is cooled and opened. The cloth has a uniform metallicgrey appearance and exhibits a gain in weight of about 0.02 gram.

A further utility for our compounds is as drying agents in which casethe compounds are incorporated in paints, varnish, printing inks,synthetic resins of the drying oil type, oil enamels and the like. Astill further utility for our compounds is their use as chemicalintermediates in the preparation of metal-containing polymeric materialsor in the preparation of new organic materials.

We claim: 1. Compounds having the formula:

. 5 ra -910M MMCO):

wherein R is a hydrocarbon group containing from one to about 8 carbonatoms, x is an integer ranging from 0 to 3, y is an integer ranging from0 to 1 and M is an alkali metal.

2. Cyclopentadienyl carboxylic acid manganese tricarbonyl,

3. Compounds having the formula:

RAJ-OH wherein R is a hydrocarbon group containing from about one toabout 8 carbon atoms, x is an integer ranging from to 3 and y in aninteger ranging from 0 to 1.

References Cited Cais et al.: Chemistry and Industry, (London), (Feb.20, 1960), p. 202.

Having fully defined the novel compounds of our invention, their mode ofpreparation and their many utilities, we desire to be limited onlywithin the lawful scope of the appended claims.

TOBIAS E. LEVOW, Primary Examiner. A. P. DEMERS, Assistant Examiner.

1. COMPOUNDS HAVING THE FORMULA: